CN103682356B - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents

A kind of anode material for lithium-ion batteries and preparation method thereof Download PDF

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CN103682356B
CN103682356B CN201210346551.4A CN201210346551A CN103682356B CN 103682356 B CN103682356 B CN 103682356B CN 201210346551 A CN201210346551 A CN 201210346551A CN 103682356 B CN103682356 B CN 103682356B
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lithium
fast
anode
ion batteries
ionic conductor
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CN103682356A (en
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叶海林
张光辉
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华为技术有限公司
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

Embodiments provide a kind of anode material for lithium-ion batteries, including positive electrode active materials and the fast-ionic conductor layer and the conductive polymer coating that are coated on surface of positive electrode active material, the constituent of fast-ionic conductor layer is the fast-ionic conductor Li of garnet structure5+x+yN3‑xM2‑yO12, wherein, N is one or more in La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y;M is one or more in Ta, Nb and V;0≤x≤2,0≤y≤1.This anode material for lithium-ion batteries not only has higher charging potential, makes capacity of lithium ion battery be substantially improved, and can be effectively improved cyclical stability and the life-span of lithium ion battery, it is achieved fast charging and discharging.The embodiment of the present invention additionally provides the preparation method of this anode material for lithium-ion batteries.

Description

A kind of anode material for lithium-ion batteries and preparation method thereof

Technical field

The present invention relates to field of lithium ion battery, particularly relate to a kind of anode material for lithium-ion batteries and system thereof Preparation Method.

Background technology

In numerous battery products, lithium ion battery due to have light weight, volume is little, running voltage is high, Energy density is high, output is big, charge efficiency is high, memory-less effect, the advantage such as have extended cycle life are subject to The close attention of people, is widely used in the field such as mobile phone, notebook computer.

In recent years, due to improving constantly of mobile device and communication appliance performance, close to the energy of lithium ion battery Degree, cycle life, High-current output input performance etc. is had higher requirement, and the most business-like contains The actually used specific capacity of lithium transition-metal oxide positive electrode is only about 1/2nd of theoretical specific capacity, This is primarily due to this positive electrode when charging/discharging voltage scope 3.0~4.2V circulates, and performance is only the most stable , and if improve charging voltage (such as more than 4.4V), the specific energy of material can be significantly improved, but Now the cycle performance of material is substantially decayed, cause decay principal element be: (1) is at high-voltage charge shape Under state, transition metal ions active in positive electrode can leave material body, enters electrolyte, just Active component in the material of pole gradually decreases, and cycle performance is gradually decayed;(2) currently used electrolyte contains Generally in acidity when having a minor amount of water, positive electrode surface can with electrolyte there is slowly effect, make positive pole material Material performance gradually decays.

For solving the problems referred to above, patent (CN101834289) disclose the lithium of a kind of oxide coated on surface from The preparation method of sub-cell positive material, by MgO, Al2O3、TiO2、ZrO2It is coated on Deng metal-oxide Surface of positive electrode active material, but, these metal-oxides the most do not have good electric conductivity, cause positive pole Materials conductive is less able, increases the internal resistance of cell, have impact on battery discharge multiplying power, reduces lithium battery Chemical property.Patent (CN101156260A) discloses the anode of secondary lithium battery of coated with fluorine compound and lives Property material and preparation method thereof.In this patent, the fluoride layer of positive electrode active materials cladding inhibits electrolyte Fluohydric acid. and the reaction of active substance, thus reduce battery capacity attenuation in charge and discharge cycles, but bag Coating selected species is AlF3、ZnF3、KF、NaF、CaF2、NiF2Deng fluorine compounds, they are not The good conductor of lithium ion, is coated on surface of active material by above-mentioned substance, and lithium ion is in this clad Diffusion velocity is slow, have impact on embedding and the deintercalation ability of lithium ion, adds the internal resistance of battery, reduce lithium The chemical property of battery.

Therefore, while improving cycle performance of lithium ion battery, in order to improve the chemical property of lithium battery, It is badly in need of seeking a kind of there is excellent lithium ion conduction ability and the positive electrode of conductive capability simultaneously.

Summary of the invention

In consideration of it, embodiment of the present invention first aspect provides a kind of anode material for lithium-ion batteries, just to solve Pole active material easily reacts with electrolyte, and under high voltage, lithium battery chemical property is the best, has relatively low Durability and the problem of cycle performance.Embodiment of the present invention second aspect is just providing a kind of lithium ion battery The preparation method of pole material.

First aspect, embodiments provides a kind of anode material for lithium-ion batteries, including positive-active material Expecting and be coated on fast-ionic conductor layer and the conductive polymer coating of surface of positive electrode active material, described conduction is gathered Compound layer is coated on described fast-ionic conductor layer surface, and the constituent of described fast-ionic conductor layer is garnet The fast-ionic conductor Li of structure5+x+yN3-xM2-yO12, wherein, N is La, Al, Sr, Sc, Cr, Ba, Fe, One or more in Mo and Y;M is one or more in Ta, Nb and V;0≤x≤2,0≤y ≤1。

Compared with prior art, the anode material for lithium-ion batteries that the embodiment of the present invention provides, is at positive-active Outer surface has been coated with fast-ionic conductor layer and conductive polymer coating, conductive polymer coating be coated on soon from Sub-conductor layer surface, wherein, the constituent of fast-ionic conductor layer is the fast ion guide of novel garnet structure Body Li5+x+yN3-xM2-yO12, wherein, N is in La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y One or more;M is one or more in Ta, Nb and V;0≤x≤2,0≤y≤1.This newly The fast-ionic conductor of type garnet structure has Stability Analysis of Structures, high temperature resistant, high voltage withstanding premium properties of Denging, tool There is higher lithium ion conductivity (> 10-3And lithium ion transference number (approximating 1), and and electrode active S/cm) Property material has the good compatibility, therefore, as material modified, this kind of fast-ionic conductor is coated on positive pole Surface of active material, not only can effectively stop positive active material to react with electrolyte, moreover it is possible to effectively to carry The lithium ion conduction ability of high positive electrode, improves the charging potential of positive electrode.Generally, fast-ionic conductor The electric conductivity of material includes two kinds: electron conduction and lithium ion conductive, although fast-ionic conductor has relatively Strong lithium ion conductive, but its electron conduction is relatively low, thus affect the fast charging and discharging of lithium ion battery Performance.Therefore, in order to improve the electric conductivity of positive electrode, the embodiment of the present invention is at fast-ionic conductor layer table Bread covers one layer of conductive polymer coating, and the conducting polymer being coated with is respectively provided with excellent electronic conductivity, Thus the electric conductivity of positive electrode can be effectively improved, reduce internal resistance, finally make positive electrode have good Lithium ion conduction ability and electric conductivity, make lithium ion battery realize fast charging and discharging.

It addition, conducting polymer has backbone, be coated on while conductive polymer coating even compact can be made soon from On sub-conductor layer, under high voltages, positive electrode active materials can be protected further not react with electrolyte.

Preferably, during the material of conductive polymer coating is polyaniline, polypyrrole, polythiophene, polyethylene glycol oxide One or more, or the copolymer formed by the monomer of two or more above-mentioned polymer.

Preferably, the thickness of fast-ionic conductor layer is 5~2500nm.

Preferably, the mass ratio of positive electrode active materials, fast-ionic conductor layer and conductive polymer coating is (80~99.8): (0.2~10): (0~10).

Preferably, positive electrode active materials is LiCoO2、LiNiO2、LiNi0.5Mn1.5O4And LiMeaNibCocO2 In one or more, wherein, one or more in Al, Mn, Cu, Mg and the Fe of M, a+b+c=1.

The anode material for lithium-ion batteries that embodiment of the present invention first aspect provides, at positive electrode active materials outer surface It is coated with fast-ionic conductor layer and conductive polymer coating, not only can effectively stop positive active material and electrolysis Liquid reacts, moreover it is possible to be effectively improved lithium ion conduction ability and the electric conductivity of positive electrode, is just improving The charging potential of pole material, makes lithium ion battery cyclical stability and life-span improve, and realizes fast charging and discharging.

Second aspect, embodiments provides the preparation method of a kind of above-mentioned anode material for lithium-ion batteries, Comprise the following steps:

(1) by cladding raw material lithium source, N source, M source and positive electrode active materials to be covered in deionized water Dispersed with stirring is uniform, makes precursor pulp;

Described cladding raw material lithium source is: in Lithium hydrate, lithium carbonate, lithium nitrate, lithium chloride and lithium acetate Plant or several;

Described N source, M source are respectively containing in the oxide of N, M, nitrate, chloride and hydroxide One or more;

Described N is one or more in La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y;Described M be Ta, Nb and V one or several in;

(2) the described precursor pulp obtained is carried out roasting, obtain described in be coated with fast-ionic conductor layer Anode material for lithium-ion batteries;

The fast-ionic conductor that constituent is garnet structure of described fast-ionic conductor layer Li5+x+yN3-xM2-yO12, wherein, N is in La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y Plant or several;M is one or more in Ta, Nb and V;0≤x≤2,0≤y≤1;

(3) the above-mentioned anode material for lithium-ion batteries being coated with fast-ionic conductor layer is joined in Bronsted acid stir Mix, add conducting polymer monomer, add oxidant, under inert gas shielding, at a temperature of-5~25 DEG C, Continuously stirred reaction 2~after 12 hours, stops stirring, filters, and washing is dried, obtains lithium ion battery Positive electrode, described anode material for lithium-ion batteries includes described positive electrode active materials and is coated on described positive pole The described fast-ionic conductor layer of surface of active material and conductive polymer coating, described conductive polymer coating is coated with On described fast-ionic conductor layer surface.

In step (1), positive electrode active materials is LiCoO2、LiNiO2、LiNi0.5Mn1.5O4With LiMeaNibCocO2In one or more, wherein, M in Al, Mn, Cu, Mg and the Fe one Plant or several, a+b+c=1.

In step (2), during described roasting, it is warmed up to 600~900 DEG C with the programming rate of 4~10 DEG C/min, Furnace cooling after being incubated 3~12 hours.Preferably, sintering temperature is 600~800 DEG C.

Preferably, the mass ratio of positive electrode active materials, fast-ionic conductor layer and conductive polymer coating is (80~99.8): (0.2~10): (0~10).

Preferably, the thickness of fast-ionic conductor layer is 5~2500nm.

In step (3), described Bronsted acid be hydrochloric acid, sulphuric acid, perchloric acid, phosphoric acid, nitric acid, to methylbenzene Sulfonic acid or DBSA, the concentration of described Bronsted acid is 0.1~2mol/L.

In step (3), described conducting polymer monomer is in aniline, pyrroles, thiophene and ethylene oxide Plant or several;Described conducting polymer monomer is 1:1~1:10 with the mol ratio of described Bronsted acid.

In step (3), described oxidant is Ammonium persulfate., potassium hyperchlorate or ferric chloride;Described oxidant It is 0.25:1~2:1 with the mol ratio of described conducting polymer monomer.

Preferably, one or more during noble gas is nitrogen, argon and helium.

Wherein, about the concrete narration of fast-ionic conductor layer and conductive polymer coating as it was noted above, the most no longer Repeat.

The preparation method of the anode material for lithium-ion batteries that embodiment of the present invention second aspect provides, technique is simple, The anode material for lithium-ion batteries prepared by the method, by positive electrode active materials outer surface cladding soon from Sub-conductor layer and conductive polymer coating, not only can effectively prevent positive active material and electrolyte to occur anti- Should, also it is effectively increased lithium ion conduction ability and the electric conductivity of positive electrode, improves positive electrode Charging potential, make lithium ion battery cyclical stability and life-span be improved, and achieve lithium ion battery Fast charging and discharging.

The advantage of the embodiment of the present invention will partly illustrate, and a part according to description is It will be apparent that or can be known by the enforcement of the embodiment of the present invention.

Accompanying drawing explanation

The button cell that the A4 that Fig. 1 A1 prepared by the embodiment of the present invention 1 provides with comparative example 1 makes, In the range of 3.0~4.5V, the specific discharge capacity under 0.2C-cycle-index comparison diagram;

The button cell that the A4 that Fig. 2 A2 prepared by the embodiment of the present invention 2 provides with comparative example 1 makes, In the range of 3.0~4.5V, the specific discharge capacity under 0.2C-cycle-index comparison diagram;

The button cell that the A5 that Fig. 3 A3 prepared by the embodiment of the present invention 3 provides with comparative example 2 makes, In the range of 3.0~4.5V, the specific discharge capacity under 0.2C-cycle-index comparison diagram;

The lithium ion battery that the A4 that Fig. 4 A1 prepared by the embodiment of the present invention 1 provides with comparative example 1 makes, In the range of 3.0~4.4V, the specific discharge capacity under 1C/1C charge and discharge cycles-cycle-index comparison diagram;

The lithium ion battery that the A5 that Fig. 5 A3 prepared by the embodiment of the present invention 3 provides with comparative example 2 makes, In the range of 3.0~4.4V, the specific discharge capacity under 1C/1C charge and discharge cycles-cycle-index comparison diagram.

Detailed description of the invention

The following stated is the preferred implementation of the embodiment of the present invention, it is noted that general for the art For logical technical staff, on the premise of without departing from embodiment of the present invention principle, it is also possible to make some improvement And retouching, these improvements and modifications are also considered as the protection domain of the embodiment of the present invention.

Embodiment of the present invention first aspect provides a kind of anode material for lithium-ion batteries, to solve positive-active material Material easily reacts with electrolyte, and under high voltage, lithium battery chemical property is the best, has relatively low durability Problem with cycle performance.Embodiment of the present invention second aspect provides a kind of anode material for lithium-ion batteries Preparation method.

First aspect, embodiments provides a kind of anode material for lithium-ion batteries, including positive-active material Expecting and be coated on fast-ionic conductor layer and the conductive polymer coating of surface of positive electrode active material, described conduction is gathered Compound layer is coated on described fast-ionic conductor layer surface, and the constituent of described fast-ionic conductor layer is garnet The fast-ionic conductor Li of structure5+x+yN3-xM2-yO12, wherein, N is La, Al, Sr, Sc, Cr, Ba, Fe, One or more in Mo and Y;M is one or more in Ta, Nb and V;0≤x≤2,0≤y ≤1。

Compared with prior art, the anode material for lithium-ion batteries that the embodiment of the present invention provides, is at positive-active Outer surface has been coated with fast-ionic conductor layer and conductive polymer coating, conductive polymer coating be coated on soon from Sub-conductor layer surface, wherein, the constituent of fast-ionic conductor layer is the fast ion guide of novel garnet structure Body Li5+x+yN3-xM2-yO12, wherein, N is in La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y One or more;M is one or more in Ta, Nb and V;0≤x≤2,0≤y≤1.This newly The fast-ionic conductor of type garnet structure has Stability Analysis of Structures, high temperature resistant, high voltage withstanding premium properties of Denging, tool There is higher lithium ion conductivity (> 10-3And lithium ion transference number (approximating 1), and and electrode active S/cm) Property material has the good compatibility, therefore, as material modified, this kind of fast-ionic conductor is coated on positive pole Surface of active material, not only can effectively stop positive active material to react with electrolyte, moreover it is possible to effectively to carry The lithium ion conduction ability of high positive electrode, improves the charging potential of positive electrode.Generally, fast-ionic conductor The electric conductivity of material includes two kinds: electron conduction and lithium ion conductive, although fast-ionic conductor has relatively Strong lithium ion conductive, but its electron conduction is relatively low, thus affect the fast charging and discharging of lithium ion battery Performance.Therefore, in order to improve the electric conductivity of positive electrode, the embodiment of the present invention is at fast-ionic conductor layer table Bread covers one layer of conductive polymer coating, and the conducting polymer being coated with is respectively provided with excellent electronic conductivity, Thus the electric conductivity of positive electrode can be effectively improved, reduce internal resistance, finally make positive electrode have good Lithium ion conduction ability and electric conductivity, make lithium ion battery realize fast charging and discharging.

It addition, conducting polymer has backbone, be coated on while conductive polymer coating even compact can be made soon from On sub-conductor layer, under high voltages, positive electrode active materials can be protected further not react with electrolyte.

Preferably, during the material of conductive polymer coating is polyaniline, polypyrrole, polythiophene, polyethylene glycol oxide One or more, or the copolymer formed by the monomer of two or more above-mentioned polymer.

Preferably, the thickness of fast-ionic conductor layer is 5~2500nm.

Preferably, the mass ratio of positive electrode active materials, fast-ionic conductor layer and conductive polymer coating is (80~99.8): (0.2~10): (0~10).

Preferably, positive electrode active materials is LiCoO2、LiNiO2、LiNi0.5Mn1.5O4And LiMeaNibCocO2 In one or more, wherein, one or more in Al, Mn, Cu, Mg and the Fe of M, a+b+c=1.

The anode material for lithium-ion batteries that embodiment of the present invention first aspect provides, at positive electrode active materials outer surface It is coated with fast-ionic conductor layer and conductive polymer coating, not only can effectively stop positive active material and electrolysis Liquid reacts, moreover it is possible to be effectively improved lithium ion conduction ability and the electric conductivity of positive electrode, is just improving The charging potential of pole material, makes lithium ion battery cyclical stability and life-span improve, and realizes fast charging and discharging.

Second aspect, embodiments provides the preparation method of a kind of above-mentioned anode material for lithium-ion batteries, Comprise the following steps:

(1) by cladding raw material lithium source, N source, M source and positive electrode active materials to be covered in deionized water Dispersed with stirring is uniform, makes precursor pulp;

Described cladding raw material lithium source is: in Lithium hydrate, lithium carbonate, lithium nitrate, lithium chloride and lithium acetate Plant or several;

Described N source, M source are respectively containing in the oxide of N, M, nitrate, chloride and hydroxide One or more;

Described N is one or more in La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y;Described M be Ta, Nb and V one or several in;

(2) the described precursor pulp obtained is carried out roasting, obtain described in be coated with fast-ionic conductor layer Anode material for lithium-ion batteries;

The fast-ionic conductor that constituent is garnet structure of described fast-ionic conductor layer Li5+x+yN3-xM2-yO12, wherein, N is in La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y Plant or several;M is one or more in Ta, Nb and V;0≤x≤2,0≤y≤1;

(3) the above-mentioned anode material for lithium-ion batteries being coated with fast-ionic conductor layer is joined in Bronsted acid stir Mix, add conducting polymer monomer, add oxidant, under inert gas shielding, at a temperature of-5~25 DEG C, Continuously stirred reaction 2~after 12 hours, stops stirring, filters, and washing is dried, obtains lithium ion battery Positive electrode, described anode material for lithium-ion batteries includes described positive electrode active materials and is coated on described positive pole The described fast-ionic conductor layer of surface of active material and conductive polymer coating, described conductive polymer coating is coated with On described fast-ionic conductor layer surface.

In step (1), positive electrode active materials is LiCoO2、LiNiO2、LiNi0.5Mn1.5O4With LiMeaNibCocO2In one or more, wherein, M in Al, Mn, Cu, Mg and the Fe one Plant or several, a+b+c=1.

In step (2), during described roasting, it is warmed up to 600~900 DEG C with the programming rate of 4~10 DEG C/min, Furnace cooling after being incubated 3~12 hours.Preferably, sintering temperature is 600~800 DEG C.

Preferably, the mass ratio of positive electrode active materials, fast-ionic conductor layer and conductive polymer coating is (80~99.8): (0.2~10): (0~10).

Preferably, the thickness of fast-ionic conductor layer is 5~2500nm.

In step (3), described Bronsted acid be hydrochloric acid, sulphuric acid, perchloric acid, phosphoric acid, nitric acid, to methylbenzene Sulfonic acid or DBSA, the concentration of described Bronsted acid is 0.1~2mol/L.

In step (3), described conducting polymer monomer is in aniline, pyrroles, thiophene and ethylene oxide Plant or several;Described conducting polymer monomer is 1:1~1:10 with the mol ratio of described Bronsted acid.

Wherein, the anode material for lithium-ion batteries being coated with fast-ionic conductor layer is joined in Bronsted acid and stirs, The time of stirring is 30~180 minutes, after adding conducting polymer monomer, stirs 30~180 minutes.

Through the anode material for lithium-ion batteries being coated with fast-ionic conductor layer that step (2) obtains, adding Before in Bronsted acid, grinding operation can be first passed through, and sieve as required and sub-elect required positive pole material Material.

In step (3), described oxidant is Ammonium persulfate., potassium hyperchlorate or ferric chloride;Described oxidant It is 0.25:1~2:1 with the mol ratio of described conducting polymer monomer.

Preferably, one or more during noble gas is nitrogen, argon and helium.

Wherein, about the concrete narration of fast-ionic conductor layer and conductive polymer coating as it was noted above, the most no longer Repeat.

The preparation method of the anode material for lithium-ion batteries that embodiment of the present invention second aspect provides, technique is simple, The anode material for lithium-ion batteries prepared by the method, by positive electrode active materials outer surface cladding soon from Sub-conductor layer and conductive polymer coating, not only can effectively prevent positive active material and electrolyte to occur anti- Should, also it is effectively increased lithium ion conduction ability and the electric conductivity of positive electrode, improves positive electrode Charging potential, make lithium ion battery cyclical stability and life-span be improved, and achieve lithium ion battery Fast charging and discharging.

Divide multiple embodiment that the embodiment of the present invention is further detailed below.Wherein, the present invention implements Example is not limited to following specific embodiment.In the range of constant principal right, can change by suitable carrying out Implement.

Embodiment one

The preparation method of a kind of anode material for lithium-ion batteries, comprises the following steps:

(1) Lithium hydrate 8g, lanthana 18.6g, tantalum oxide 8.5g, nickle cobalt lithium manganate are weighed (LiNi0.5Co0.2Mn0.3O2) 2000g, it is placed in four and stirs equipped with in the 10L agitator tank of 1500g deionized water Mix uniformly, form precursor pulp;

(2) the above-mentioned precursor pulp obtained being carried out roasting, roasting standard is: be warmed up to 8 DEG C/min 600 DEG C, it is incubated 8 hours, furnace cooling, obtain the fast ion guide of Surface coating a layer thickness about 60nm Nickle cobalt lithium manganate (the LiNi of body layer0.5Co0.2Mn0.3O2), the biomolecule expressions of its fast-ionic conductor is Li5La3Ta2O12

(3) the above-mentioned nickel-cobalt lithium manganate material being coated with fast-ionic conductor layer being joined 1.6L concentration is The dilute hydrochloric acid of 0.2mol/L stirs 30 minutes, adds by mol ratio 1:1 of polymer monomer with Bronsted acid Conducting polymer monomer aniline 30g stirs 30 minutes, by the mol ratio 0.25 of oxidant Yu polymer monomer: 1 adds Ammonium persulfate. 18.4g, continues stirring, and nitrogen is protected, and after reacting 10 hours, stops stirring, mistake Filter, washing, then it is dried, obtains the anode material for lithium-ion batteries of the present embodiment, be designated as A1.

Embodiment two

The preparation method of a kind of anode material for lithium-ion batteries, comprises the following steps:

(1) Lithium hydrate 10g, lanthana 13g, tantalum oxide 8.8g, niobium oxide 5.3g, strontium nitrate are weighed 8.4g, nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2) 3000g, it is placed in four equipped with 2000g deionized water 10L agitator tank stirs, forms precursor pulp;

(2) the above-mentioned precursor pulp obtained being carried out roasting, roasting standard is: be warmed up to 8 DEG C/min 600 DEG C, it is incubated 8 hours, furnace cooling, obtain the fast ion guide of Surface coating a layer thickness about 100nm Nickle cobalt lithium manganate (the LiNi of body layer0.5Co0.2Mn0.3O2), the biomolecule expressions of its fast-ionic conductor is Li6SrLa2TaNbO12

(3) the above-mentioned nickel-cobalt lithium manganate material being coated with fast-ionic conductor layer being joined 1.8L concentration is The dilute sulfuric acid of 0.5mol/L stirs 30 minutes, adds by mol ratio 1:5 of polymer monomer with Bronsted acid Conducting polymer monomer aniline 12g stirs 30 minutes, by mol ratio 1:1 of oxidant Yu polymer monomer Adding ferric chloride 48g, continue stirring, nitrogen is protected, and after reacting 8 hours, stops stirring, filters, Washing, is then dried, obtains the anode material for lithium-ion batteries of the present embodiment, be designated as A2.

Embodiment three

The present embodiment differs only in embodiment one, by positive electrode active materials nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2) it is replaced with cobalt acid lithium (LiCoO2), the conducting polymer monomer aniline of addition is replaced with Pyrroles, obtains the anode material for lithium-ion batteries of the present embodiment, is designated as A3.

Embodiment four

The preparation method of a kind of anode material for lithium-ion batteries, comprises the following steps:

(1) Lithium hydrate 8g, aluminium hydroxide 4.5g, tantalum oxide 8.5g, nickle cobalt lithium manganate are weighed (LiNi0.5Co0.2Mn0.3O2) 4000g, it is placed in four and stirs equipped with in the 15L agitator tank of 3000g deionized water Mix uniformly, form precursor pulp;

(2) the above-mentioned precursor pulp obtained being carried out roasting, roasting standard is: be warmed up to 8 DEG C/min 700 DEG C, it is incubated 8 hours, furnace cooling, obtain the fast ion guide of Surface coating a layer thickness about 25nm Nickle cobalt lithium manganate (the LiNi of body layer0.5Co0.2Mn0.3O2), the biomolecule expressions of its fast-ionic conductor is Li5Al3Ta2O12

(3) the above-mentioned nickel-cobalt lithium manganate material being coated with fast-ionic conductor layer being joined 2L concentration is The nitric acid of 0.1mol/L stirs 60 minutes, adds by mol ratio 1:1 of polymer monomer with Bronsted acid and lead Electric polymer monomer thiophene 15g stirs 60 minutes, by mol ratio 2:1 of oxidant and polymer monomer again Adding potassium hyperchlorate 28g, continue stirring, nitrogen is protected, and after reacting 8 hours, stops stirring, filters, wash Wash, be then dried, obtain the anode material for lithium-ion batteries of the present embodiment, be designated as A6.

Embodiment five

The preparation method of a kind of anode material for lithium-ion batteries, comprises the following steps:

(1) Lithium hydrate 10g, lanthana 13g, vanadium oxide 3.6g, niobium oxide 5.3g, barium nitrate are weighed 10.3g, nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2) 1200g, it is placed in four equipped with 2000g deionized water 10L agitator tank in stir formation precursor pulp;

(2) the above-mentioned precursor pulp obtained being carried out roasting, roasting standard is: be warmed up to 8 DEG C/min 600 DEG C, it is incubated 8 hours, furnace cooling, obtain the fast ion of Surface coating a layer thickness about 2500nm Nickle cobalt lithium manganate (the LiNi of conductor layer0.5Co0.2Mn0.3O2), the biomolecule expressions of its fast-ionic conductor is Li6BaLa2VNbO12

(3) the above-mentioned nickel-cobalt lithium manganate material being coated with fast-ionic conductor layer being joined 1.6L concentration is The p-methyl benzenesulfonic acid of 2mol/L stirs 30 minutes, by mol ratio 1:10 of polymer monomer Yu Bronsted acid Add conducting polymer monomer aniline 30g to stir 30 minutes, by the mol ratio 1 of oxidant Yu polymer monomer: 2 add Ammonium persulfate. 36.8g, continue stirring, and nitrogen is protected, and after reacting 5 hours, stop stirring, mistake Filter, washing, then it is dried, obtains the anode material for lithium-ion batteries of the present embodiment, be designated as A7.

Embodiment six

The present embodiment differs only in embodiment five, by positive electrode active materials nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2) it is replaced with cobalt acid lithium (LiNiO2), the conducting polymer monomer aniline of addition is replaced with Pyrroles, obtains the anode material for lithium-ion batteries of the present embodiment, is designated as A8.

Comparative example one

Use the nickle cobalt lithium manganate (LiNi used in embodiment one0.5Co0.2Mn0.3O2) positive electrode active materials, no Carry out being coated with fast-ionic conductor and conducting polymer, be designated as A4.

Comparative example two

Use the cobalt acid lithium (LiCoO used in embodiment three2) positive electrode active materials, do not carry out being coated with fast ion Conductor and conducting polymer, be designated as A5.

Effect example

Beneficial effect for bringing embodiment of the present invention technical scheme provides powerful support for, by above example The anode material for lithium-ion batteries prepared with comparative example is assembled into lithium ion battery, and provides following circulation volume Performance test:

1, anode material for lithium-ion batteries A1, A2, A3 of above example being prepared and comparative example provide A4, A5 be assembled into button cell as follows: by positive electrode and conductive carbon, Kynoar (PVDF) Join in N-methyl-2 ketopyrrolidine (NMP) for 90:5:5 in mass ratio, be uniformly mixed and made into positive pole Slurry, and be coated on plus plate current-collecting body and form positive pole after drying, with lithium sheet as negative pole, group in glove box Dress up button cell.

By the above-mentioned button cell being assembled into by A1, A2, A3 and the button cell being assembled into by A4, A5, In 3.0~4.5V voltage ranges, under 0.2C, carry out charge-discharge test.

Fig. 1 is the button cell that positive electrode A1 with A4 makes, in the range of 3.0~4.5V, under 0.2C Specific discharge capacity-cycle-index comparison diagram;Fig. 2 is the button cell that positive electrode A2 with A4 makes, In the range of 3.0~4.5V, the specific discharge capacity under 0.2C-cycle-index comparison diagram.Result shows, surface is wrapped Cover the nickle cobalt lithium manganate (LiNi of fast-ionic conductor and conducting polymer0.5Co0.2Mn0.3O2) circulation of positive electrode Performance significantly improves.

Fig. 3 is the button cell that positive electrode A3 with A5 makes, in the range of 3.0~4.5V, under 0.2C Specific discharge capacity-cycle-index comparison diagram.Result shows, Surface coating fast-ionic conductor and conducting polymer Cobalt acid lithium (LiCoO2) cycle performance of positive electrode significantly improves.

2, by above example prepare anode material for lithium-ion batteries A1, A3 and comparative example provide A4, A5 is assembled into lithium ion battery: by positive electrode with conductive carbon, Kynoar (PVDF) be in mass ratio 90:5:5 joins in N-methyl-2 ketopyrrolidine (NMP), is uniformly mixed and made into anode sizing agent, and is coated with Cloth forms positive pole on plus plate current-collecting body after drying, by Delanium and conductive carbon, butadiene-styrene rubber (SBR), carboxylic Methylcellulose (CMC) is uniformly mixed and made into cathode size for 90:5:2:3 in mass ratio in water, and is coated with Cloth forms negative pole on negative current collector after drying, positive pole, negative pole and isolating membrane is wound with common process, Lithium is prepared through terminal welding, packaging foil encapsulation, injection nonaqueous electrolytic solution, encapsulation chemical conversion, molding of bleeding Ion battery.Wherein, described nonaqueous electrolytic solution is ethylene carbonate: methyl ethyl carbonate: carbonic acid diethyl The mixed solution that ester is formed with volume ratio for 1:1:1, wherein contains the lithium hexafluoro phosphate of 1 mole.By upper The lithium ion battery stating the lithium ion battery being assembled into by A1, A3 and be assembled into by A4, A5,3.0~ In 4.5V voltage range, under 1C, carry out charge-discharge test.

Fig. 4 is the lithium ion battery that positive electrode A1 with A4 makes, in the range of 3.0~4.4V, and 1C/1C Specific discharge capacity under charge and discharge cycles-cycle-index comparison diagram, figure 4, it is seen that use surface bag Nickle cobalt lithium manganate (the LiNi covered0.5Co0.2Mn0.3O2) positive electrode A1 lithium ion battery through 325 times circulation After, its capacity keeps reaching 77%;And use the most surface coated nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2) positive electrode A4 lithium ion battery 60 circulate after, capacity has been reduced to 84%.Result illustrates: nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2) positive electrode is through fast-ionic conductor and leads After electric polymer cladding, cycle performance under high voltages is significantly improved.

Fig. 5 is the lithium ion battery that positive electrode A3 with A5 makes, in the range of 3.0~4.4V, and 1C/1C Specific discharge capacity under charge and discharge cycles-cycle-index comparison diagram, from figure 5 it can be seen that use surface bag The cobalt acid lithium (LiCoO covered2) positive electrode A3 lithium ion battery through 250 times circulate after, its capacity protect Hold and can reach 75%;And use the most surface coated cobalt acid lithium (LiCoO2) lithium-ion electric of positive electrode A5 After pond is circulated at 60, capacity has been reduced to 75%.Result illustrates: cobalt acid lithium (LiCoO2) positive electrode warp After crossing fast-ionic conductor and conducting polymer cladding, cycle performance under high voltages is significantly improved.

Claims (10)

1. an anode material for lithium-ion batteries, it is characterized in that, including positive electrode active materials and the fast-ionic conductor layer and the conductive polymer coating that are coated on described surface of positive electrode active material, described conductive polymer coating is coated on described fast-ionic conductor layer surface, the fast-ionic conductor Li that constituent is garnet structure of described fast-ionic conductor layer5+x+yN3-xM2-yO12, wherein, N is one or more in La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y;M is one or more in Ta, Nb and V;0≤x≤2,0≤y≤1.
2. a kind of anode material for lithium-ion batteries as claimed in claim 1, it is characterized in that, the material of described conductive polymer coating is one or more in polyaniline, polypyrrole, polythiophene and polyethylene glycol oxide, or the copolymer formed by the monomer of two or more above-mentioned polymer.
3. a kind of anode material for lithium-ion batteries as claimed in claim 1, it is characterised in that the thickness of described fast-ionic conductor layer is 5~2500nm.
4. a kind of anode material for lithium-ion batteries as claimed in claim 1, it is characterized in that, the mass ratio of described positive electrode active materials, fast-ionic conductor layer and conductive polymer coating is (80~99.8): (0.2~10): (0~10).
5. a kind of anode material for lithium-ion batteries as claimed in claim 1, it is characterised in that described positive electrode active materials is LiCoO2、LiNiO2、LiNi0.5Mn1.5O4And LiMeaNibCocO2In one or more, wherein, one or more in Al, Mn, Cu, Mg and Fe of Me, a+b+c=1.
6. the preparation method of an anode material for lithium-ion batteries, it is characterised in that comprise the following steps:
(1) by uniform to cladding raw material lithium source, N source, M source and positive electrode active materials to be covered dispersed with stirring in deionized water, precursor pulp is made;
Described cladding raw material lithium source is: one or more in Lithium hydrate, lithium carbonate, lithium nitrate, lithium chloride and lithium acetate;
Described N source, M source are respectively containing one or more in the oxide of N, M, nitrate, chloride and hydroxide;
Described N is one or more in La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y;Described M is one or more of Ta, Nb and V;
(2) the described precursor pulp obtained is carried out roasting, obtain described in be coated with the anode material for lithium-ion batteries of fast-ionic conductor layer;
The fast-ionic conductor Li that constituent is garnet structure of described fast-ionic conductor layer5+x+yN3-xM2-yO12, wherein, N is one or more in La, Al, Sr, Sc, Cr, Ba, Fe, Mo and Y;M is one or more in Ta, Nb and V;0≤x≤2,0≤y≤1;
(3) the above-mentioned anode material for lithium-ion batteries being coated with fast-ionic conductor layer is joined in Bronsted acid and stir, add conducting polymer monomer, add oxidant, under inert gas shielding, at a temperature of-5~25 DEG C, continuously stirred reaction 2~after 12 hours, stop stirring, filter, washing, it is dried, obtain anode material for lithium-ion batteries, described anode material for lithium-ion batteries includes described positive electrode active materials and is coated on described fast-ionic conductor layer and the conductive polymer coating of described surface of positive electrode active material, described conductive polymer coating is coated on described fast-ionic conductor layer surface.
7. the preparation method of anode material for lithium-ion batteries as claimed in claim 6, it is characterised in that
It is warmed up to 600~900 DEG C with the programming rate of 4~10 DEG C/min, furnace cooling after being incubated 3~12 hours during described roasting.
8. the preparation method of anode material for lithium-ion batteries as claimed in claim 6, it is characterised in that
Described Bronsted acid is hydrochloric acid, sulphuric acid, perchloric acid, phosphoric acid, nitric acid, p-methyl benzenesulfonic acid or DBSA, and the concentration of described Bronsted acid is 0.1~2mol/L.
9. the preparation method of anode material for lithium-ion batteries as claimed in claim 6, it is characterised in that
Described conducting polymer monomer is one or more in aniline, pyrroles, thiophene and ethylene oxide;Described conducting polymer monomer is 1:1~1:10 with the mol ratio of described Bronsted acid.
10. the preparation method of anode material for lithium-ion batteries as claimed in claim 6, it is characterised in that described oxidant is Ammonium persulfate., potassium hyperchlorate or ferric chloride;Described oxidant is 0.25:1~2:1 with the mol ratio of described conducting polymer monomer.
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